CN1378564A - Acrylic block copolymer pigment dispersants containing beterocyclic groups - Google Patents

Acrylic block copolymer pigment dispersants containing beterocyclic groups Download PDF

Info

Publication number
CN1378564A
CN1378564A CN00813941A CN00813941A CN1378564A CN 1378564 A CN1378564 A CN 1378564A CN 00813941 A CN00813941 A CN 00813941A CN 00813941 A CN00813941 A CN 00813941A CN 1378564 A CN1378564 A CN 1378564A
Authority
CN
China
Prior art keywords
composition
segment
heterocyclic group
group
block copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN00813941A
Other languages
Chinese (zh)
Other versions
CN1175007C (en
Inventor
J·胡伊布雷希茨
D·C·克雷特
R·韦夫洛伊特
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of CN1378564A publication Critical patent/CN1378564A/en
Application granted granted Critical
Publication of CN1175007C publication Critical patent/CN1175007C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant

Abstract

Acrylic AB block copolymers prepared by group transfer polymerization that are useful as pigment dispersant, characterized by mononuclear or dinuclear heterocyclic groups bonded to the highly polar anchoring A segment of the block copolymer backbone to facilitate attachment on a pigment surface and improve dispersant efficiency in solvent-borne paint systems.

Description

The acrylic block copolymer pigment dispersants that contains heterocyclic group
Background of invention
The present invention relates to a kind of pigment dispersing agent, more specifically, it relates to a kind of pigment dispersing agent that comprises acrylic block copolymer, and this segmented copolymer prepares by group transfer polymerization, wherein adopt in the polarity heterocyclic group modification block, with promote with surface of pigments on be connected.
Acrylic block copolymer pigment dispersants by the preparation of group transfer polymerization (GTP) technology is known.Typically, such dispersion agent is AB, ABA or BAB type.All types all contains at least one and is called A segmental polarity segment, with promote with surface of pigments be connected and at least one is called the nonpolar segment of B segmental, with strengthen pigment particles in dispersion spatial stability and prevent to flocculate.In addition, can adopt the group modified A block of side pole to increase validity, for example, instruction is such in people's such as Hutchins U.S. Patent No. 4,656,226.Such composition also can adopt the hydroxy functional group preparation in the B segment, so that carry out crosslinkedly in final thermosetting varniss composition, dispersion agent becomes the part of network structure like this; Yet the performance of dispersion agent may be subjected to negative impact.
Research and develop to improve the performance of pigment dispersing agent always, particularly seek new acrylic block copolymer dispersion agent, this dispersion agent is very suitable at various liquid mediums, particularly dispersible solid pigment in the solvent-borne type paint systems.
Summary of the invention
The invention provides a kind of composition that is suitable for use as pigment dispersing agent, said composition comprises the acrylic block copolymer by GTP polymerization preparation, this segmented copolymer contains the relative nonpolar B segment with at least one of A segment of at least one relative polarity that is bonded together, each segment contains the preferred main chain of mainly being made up of polymeric methacrylic monomeric unit, contain the one or more polarity heterocyclic groups that are bonded on it with this segments A, these heterocyclic groups are selected from monokaryon or double-core five and/or six-ring, these rings comprise one or more nitrogen-atoms and optional oxygen and/or sulphur atoms as loop section, and wherein ring comprises at least one and is free of attachment to nitrogen-atoms on the hydrogen atom.These heterocyclic groups are as side group, and it can be directly connected on the A segment or by urethane and/or urea key and introduce.This segmented copolymer preferably also comprises hydroxy functional group at one of A and B segment or both.Also preferred this segmented copolymer is the AB type.
The present invention is based on following discovery: even under the situation that has hydroxy functional group to exist on the main polymer chain, this hydroxy functional group is generally used for crosslinked purpose, and improving consistency with other binder component that in final paint composite, exists, the introducing of above-mentioned heterocyclic group on the A segment can prepare the acrylic block copolymer with excellent pigment dispersing agent performance.
Preferred heterocyclic group is triazole, pyrimidine, imidazoles, pyridine, morpholine, tetramethyleneimine, piperazine, piperidines, benzoglyoxaline, benzothiazole and/or triazine.These heterocyclic groups can be unsubstitutedly maybe can comprise following substituting group: as alkyl, aryl, halogen and alkoxyl group.Detailed Description Of The Invention
The GTP technology can, and be preferred for producing acrylic block copolymer of the present invention.Known GTP technology is used to produce low molecular weight propylene acids segmented copolymer, the number-average molecular weight (M of this multipolymer n) be generally 1,300-20,000, have the molecular weight distribution of more accurate control and form distribution.This technology can form the block with low polymolecularity and even functionality and more effective dissemination is provided.The GTP technology is a technique known, and describes in detail in the U.S. Patent No. 4,656,226 of the Hutchins that authorizes on April 7th, 1987 etc., and this patent is incorporated herein by reference with the reference form at this.
According to this technology, compare with the typical any-mode of polyreaction, when the condition that controlled polymerization carries out, usually unsaturated monomer is contacted with the catalyst system that comprises silicon, tin or germanium with initiator, the polymkeric substance that can prepare substantially linear like this, this linear polymer contain the homogeneous polymer chain and have required molecular weight.At this, although the desired molecule amount of this segmented copolymer within above-mentioned scope, the preferred especially Mn of the present invention is lower than 13,000.
The acrylic block copolymer of being produced by this technology of the present invention preferably contains at least one strong relatively relative nonpolar B with at least one of polarity A segment stablizes segment, this A segment as on the surface of pigments in conjunction with side chain, this B segment has higher molecular weight usually, and it preferably contains and is useful on the functional group of reacting in the thermosetting varniss composition.Polarity A segment is reflected on the surface of pigments by acid-alkali and absorbs, and the B segment provides the deflocculate spatial stability of pigment particles simultaneously.
Generally speaking, the A segment should be: (1) can interact with surface of pigments; (2) have enough sizes so that irreversible absorption to be provided, but do not reach complete coverage pigment surface or cause the degree (M typically of B segment avalanche n=300-5,000).The B segment should be: (1) has enough sizes so that spatial stability (M typically to be provided n=1,000 or bigger); (2) with liquid dispersion medium (solvent) and substrate adhesive polymer-compatible (enough to dissolve to prevent be separated).
Be to use polystyrene standards to pass through that GPC (gel permeation chromatography) measures at all molecular weight of this indication.
The B segment as mentioned above, also preferably comprises functional group such as hydroxyl, so that carry out crosslinkedly in final thermosetting varniss composition, so that dispersion agent becomes the part of network structure, and can improve consistency with other binder component.For these groups are existed, heteropolar bond side chain (A segment) can not be substituted by other functional group, otherwise can make the pigment dispersion instability.
The inventor has been found that, the introducing of heterocyclic group has not only improved its performance as pigment dispersing agent in the above-mentioned universal class acrylic block copolymer, and even more beat allly be, even under the situation that hydroxyl is arranged in other segment and can exist at the polar solvent of formation absorption competition on the surface of pigments, such heterocyclic group can be used as effective conjugated group.
In the present invention, have been found that at first to form basic acrylic block copolymer, use following technology then, by localized functional group by the GTP technology, required heterocyclic group is connected to A directly or indirectly in conjunction with on the segment, described operation is very easy easy row.
In the preparation of basic segmented copolymer, can prepare block by any order.That is, can at first prepare A segment or B segment.In addition, although general preferred AB segmented copolymer also can prepare ABA and BAB three blocks as needs.Under any circumstance, although methacrylic ester most preferably, each segmental main chain mainly is made up of at least a polymeric methacrylic ester or acrylate.In the context of the present invention, methacrylic ester and acrylic ester unit are commonly referred to as methacrylic and acrylic monomer units at this.
More specifically, preferably from alkyl methacrylate, or the blend of alkyl methacrylate such as methyl methacrylate (MMA), butyl methacrylate (BMA), methacrylic acid 2-ethylhexyl etc. prepares the B segment.As needs, can pass through the hydroxyalkyl methacrylate monomer, as hydroxyethyl methylacrylate (HEMA), Rocryl 410 etc., introduce hydroxy functional group.Yet, before polymerization, must seal hydroxyl with avoid with GTP in the reaction of the initiator that uses.The possible mode of sealing hydroxyl is to adopt the trimethyl silyl or derivatives thereof.Can be after block polymer forms, by the hydroxyl deblocking of hydrolysis with sealing.Usually in acrylic block copolymer, need hydroxyl.Acrylic block copolymer generally should have the hydroxyl value of 5-120.On the other hand, the A segment needs the existence of functional group to be connected with the polarity heterocyclic group.As following in more detail as described in, epoxy functionalized methacrylic ester such as glycidyl methacrylate (GMA) etc., hydroxyl-functional methacrylic ester such as hydroxyethyl methylacrylate (HEMA) etc., with amino-functional methacrylic ester such as methacrylic acid tertiary butyl aminoethyl ester (t-BAEMA) etc., can be used as this purpose.
In the present invention, the A segment generally comprises about 2-60wt%, the preferred segmented copolymer of about 10-30wt%, and the B segment generally comprises about 40-98wt%, preferably the segmented copolymer of about 70-90wt%.
Equally in the present invention, for optimized efficient, at least about 2wt%, most preferably A segment (methyl) acrylic monomer units of 50wt% contains the heterocyclic group that is bonded on it at least.This heterocyclic group can be monokaryon or double-core five and/or six-ring, and this ring comprises one or more theheterocyclic nitrogen atoms and epoxy of choosing wantonly and/or sulphur atom and contains the theheterocyclic nitrogen atom that at least one does not comprise hydrogen atom.Term " monokaryon " refers to independently five or six-ring as used herein, term " double-core " refer to be fused to another five or six-ring on five or six-ring.Preferred heterocyclic group is triazole, pyrimidine, imidazoles, pyridine, morpholine, tetramethyleneimine, piperazine, piperidines, benzoglyoxaline, benzothiazole and/or triazine group.These groups can be unsubstitutedly maybe can comprise substituting group, as alkyl, aryl, halogen and alkoxyl group.The imdazole derivatives that preferred especially low alkyl group replaces is as glyoxal ethyline and 4-methylimidazole.
Can be by the functional group reactions that provides in Hete rocyclic derivatives and the A segment, and heterocyclic group is directly connected in conjunction with on the A segment.As the following example that provides, can heterocyclic group be placed in conjunction with on the A segment as side group by Hete rocyclic derivatives and epoxy-functional reaction.Carry out the synthetic of segmented copolymer from polymeric (methyl) acrylic monomer units, the segment of one of them generation comprises epoxy-functional, and it is described in detail in the U.S. Patent No. 4,656,226 that is issued to people such as purpose Hutchins April 7 in 1987.For example, can pass through, as the copolymerization acquisition epoxide group (embodiment 1) of glycidyl methacrylate.Then in subsequent reaction, epoxide group can with contain active hydrogen atom, as-NH-,-NH 2,-COOH and-reaction of the heterogeneous ring compound of SH.Contain two active H atoms as-NH at compound 2Situation under, the quantity that must control the glycidyl functional group is to avoid crosslinked and gelation.In the case, also can by with the reaction of monocycle oxygen derivative, at first with primary amino functional group-NH 2Modification Cheng Zhong-NH-group.The example of heterogeneous ring compound that contains active H atom is as follows:
Figure A0081394100071
Figure A0081394100072
Figure A0081394100073
Tetramethyleneimine morpholine piperidines
Figure A0081394100082
The imidazoles piperazine
Figure A0081394100083
Figure A0081394100085
2-mercaptobenzothiazole 1,2,4-triazole pyrazoles
Hete rocyclic derivatives be by epoxide group reaction in carboxyl-functional Hete rocyclic derivatives and the A segment with other possibility approach that side group is directly connected on the segmented copolymer.
Also can pass through urethane and/or urea key, introduce heterogeneous ring compound in the acrylic block copolymer indirect.For example, in mole, N-(3-aminopropyl) imidazoles can react with isophorone diisocyanate, and the intermediate imidazoles official of containing a unreacting isocyanate functional group with formation can urea, it in step subsequently with a segment in the amino reaction.Can obtain this amido functional group by as the copolymerization (embodiment 2) of tertiary butyl amino-ethyl methacrylic ester or the reaction by epoxy-functional and monoamine or ammonia.The example of monoamine is ethamine, propylamine, lauryl amine, thanomin, Yi Bingchunan and 2-amino butanol.Isocyanate-functional heterocyclic urea intermediate also can with the hydroxyl reaction on the main chain, to form the urea key.Also can form the heterocycle official energy intermediate that contains the isocyanate functional group by hydroxyl-functional Hete rocyclic derivatives and two and/or the reaction of polyisocyanates.As the 2-hydroxyethyl morpholine.Also can pass through amino-functional Hete rocyclic derivatives and cyclic carbonate, the reaction as carbonic acid ethylidene ester, propylene carbonate, carbonic acid butylidene ester, carbonic acid glyceride forms such hydroxyl-functional intermediate.Other example of vulcabond includes, but not limited to tolylene diisocyanate, hexamethylene diisocyanate, eylylene diisocyanate, diphenylmethanediisocyanate (MDI), hydrogenation MDI, trimethyl hexamethylene diisocyanate.Possible polyfunctional isocyanate is the reaction product of cyclic trimer and biuret or excess diisocyanate and polyvalent alcohol precursor.
The new heterocycle acrylic block copolymer of the present invention has shown its excellent properties as pigment dispersing agent in liquid medium, particularly, as the solvent-borne type paint systems that is used for the automobile covering with paint or covers with paint, lacquer, colour wash, etc. again, except that pigment and dispersion agent, they comprise binding agent or membrane-forming agent, organic solvent (being liquid dispersion medium) and other conventional additive.Pigment and dispersion agent can join separately in the liquid paint medium or add with the form of preferred dispersion.If employing dispersion, dispersion generally comprise pigment and the dispersion medium (solvent) compatible with the liquid paint medium.
By specific embodiment the present invention is described in more detail now.Unless otherwise indicated, all umbers and per-cent are all by weight.
Embodiment
In following embodiment 1-2, the preparation process of basic AB segmented copolymer is described, various heterocyclic groups can be connected on this multipolymer:
Before using, all monomers and solvent are stored by the 4A molecular sieve drying and under nitrogen.
The preparation of embodiment 1GMA ∥ nBMA/MMA/HEMA 5 ∥ 10/10/2 (mole meter)
3 liters of round bottom 4 neck flasks are equipped with condenser/drierite ze pipe, digital thermometer probe and N 2Inlet, mechanical stirrer and monomer addition funnel.Use N then 2Purge flask and use the heat gun drying.Adopting N 2In the time of the flushing flask, add 1016.4gTHF, 50.0g1-methoxyl group-1-trimethylsiloxy-2-methacrylic, add 2.5g1 with syringe by feed hopper, 3, the 5-trimethylbenzene.Flask is cooled to 4.8 ℃ and inject 2.5mL m-chlorobenzoic acid TBuA at the 1M of acetonitrile solution in ice bath.In 30 minutes time, add glycidyl methacrylate (GMA) (203.8g) by other feed hopper.In 25 minutes, temperature is elevated to 34 ℃, begins to cool down again to maintain the temperature at below 35 ℃ in the remaining time that adds at GMA.In the time of 40 minutes from the outset, the GMA transformation efficiency is 99.95%, removes ice bath and begins second monomer feed (B block).The main ingredient of B block be n-BMA (nBMA) (407.8g), methyl methacrylate (MMA) (287.4g) and the 2-[trimethylsiloxy] hydroxyethyl methacrylic ester (TMS-HEMA) (116.2g).In the time of 50 minutes, inject the 0.6mL catalyzer with accelerated reaction.(85 minutes) temperature is elevated to 70.2 ℃ when charging finishes.Monomeric transformation efficiency (HPLC) is at least 99.6% in the time of 208 minutes.In the time of 333 minutes from the outset, add 7.7g water and with the flask cool to room temperature.The actual solid of polymkeric substance is 47.94%, M n=4139 (theoretical values 3500), D (polymolecularity)=1.38.
The preparation of embodiment 2nBMA/MMA/HEMA ∥ t-BAEMA 10/10/2 ∥ 3 (mole meter)
3 liters of round bottom 4 neck flasks are equipped with condenser/drierite ze pipe, digital thermometer probe and N 2Inlet, mechanical stirrer and monomer addition funnel.Use N then 2Purge flask and use the heat gun drying.Adopting N 2In the time of the flushing flask, add 1100.9gTHF, 50.0g 1-methoxyl group-1-trimethylsiloxy-2-methacrylic, adopt syringe to add 2.5g1,3,5-trimethylbenzene by feed hopper.At room temperature, inject 4.8mL m-chlorobenzoic acid TBuA at the 1M of acetonitrile solution (being called catalyzer) and begin first monomer feed at this.In this embodiment at first the main ingredient of B block of preparation be n-BMA (nBMA) (408.0g), methyl methacrylate (MMA) (287.5g) and the 2-[trimethylsiloxy] hydroxyethyl methacrylic ester (TMS-HEMA) (116.7g), these components added by other feed hopper in 45 minutes.In 4 minutes, temperature is elevated to 34.5 ℃, and uses cooling bath to maintain the temperature at below 40 ℃.In the time of 160 minutes from the outset, the monomer conversion of being measured by HPLC is 99.6% at least.Remove ice bath, in the time of 205 minutes, begin second monomer feed.The main ingredient of A block be tertiary butyl aminoethyl methacrylic ester (t-BAEMA) (160.1g).When temperature reached 32.7 ℃, charging II finished in the time of 235 minutes from the outset.In the time of 335 minutes, add entry (32g) and make the response composite cool to room temperature.The actual solid of polymkeric substance is 44.81%, M n=3996 (theoretical values 3300), D=1.81.
In following embodiment 3～6, AB segmented copolymer of selecting from aforesaid embodiment and heterocyclic radical reaction are to form AB dispersion agent of the present invention.But in Comparative Examples 1, described AB segmented copolymer and tert-aliphatic amine reaction obtain being connected to the side tertiary amine functional group of multipolymer, rather than heterocycle functional group.In Comparative Examples 2, basic AB segmented copolymer is not done any modification, its object of reference as a comparison.
Embodiment 3,4 and 5 prepares heterocyclic modified AB segmented copolymer by the modification to the AB segmented copolymer of embodiment 1
In being equipped with 2 liters of round-bottomed flasks of condenser, the 1000 gram AB block copolymer solutions of embodiment 1 and 55.5 gram glyoxal ethylines (embodiment 3), 55.5 gram 4-methylimidazoles (embodiment 4) and 58.8 restrain morpholine (embodiment 5) back flow reaction 4 hours.Adopt n-butyl acetate polymers soln be diluted to 40% solid thereafter.
The AB block copolymer amount (M of embodiment 3 n) be 3800 (polymolecularity (D)=1.48), the AB block copolymer amount of embodiment 4 is 3700 (D=1.48), and the AB block copolymer amount of embodiment 5 is 5800 (D=1.48).Comparative Examples 1
For relatively using 50.7 gram 2-Mono Methyl Ethanol Amines to replace Hete rocyclic derivatives, repeat the step of embodiment 3,4 and 5.According to the U.S. Patent No. 4,656,226 of Hutchins etc., can obtain in a block, containing the AB segmented copolymer of tertiary amine group like this.Comparative Examples 2
Employing do not have modification embodiment 1 the AB segmented copolymer as a comparison.
Embodiment 6 prepares heterocyclic modified AB segmented copolymer by the modification of the AB segmented copolymer of embodiment 2
In 6 liters of round-bottomed flasks, by at room temperature stirring 10 minutes, the 1000 gram grams of 130 in the n-butyl acetates (1 mole) just-3-aminopropyl imidazoles, with 222 gram (1 mole) isophorone diisocyanate reactions that are dissolved in 387 gram n-butyl acetates, to form isocyanate-functional urea-imidazoles intermediate.This intermediate further with 2300 the gram embodiment 2 block copolymer reacting.Obtain number-average molecular weight like this and be 5600 and weight-average molecular weight be the AB segmented copolymer of imidazoles-urea modification of 10200.
The evaluation of embodiment 7 dispersing agent performances
General mixture by sand milling pigment, solvent and dispersion agent, definite proper ratio that obtains the required dispersion agent (if there is) of homogeneous dispersion shows as painted glass under optical magnification 250x, measures the dispersion agent quality with such method.On the contrary, the pigment of flocculation but presents the colored island district of interspersing relative transparent solvent zone.With the following artificial grade evaluation degree of scatter of determining that provides.
Estimate following 5 kinds of pigment: from the chestnut color r-6436 of Bayer De perylene, from the green 264-0414 of phthalocyanine (phtalocyanine) of SunChemical, from the blue bt-617-d of phthalocyanine (phtaloeyanine) of Clariant, from the carbon black 5000ii powder of Columbian chemicals with from the pinkish red rt-143-d of the quinacridone of Ciba-geigy.In evaluation, in the revolution mixing machine,, ground 15 minutes with 30 gram Ottawa sand with 3.38 grams, 40% solid polymer solution (except the sooty situation, it uses 11.25 grams), 4.5 gram pigment and 40 gram n-butyl acetates (non-polar organic solvent).
By examine under a microscope flocculation situation, estimate the flocculation situation of pigment dispersion thereafter.With represent flocculating degree (not flocculation of 0 expression, the strong flocculation of 10 expressions) from the grade of 0-10, for above-mentioned 5 kinds of pigment, the average score of different AB segmented copolymers is as follows:
The result
The AB dispersion agent The flocculation grade
Comparative Examples 2 (not having modification) ????5.5
Embodiment 3 ????0.5
Embodiment 4 ????0.5
Embodiment 5 ????2
Comparative Examples 1 (tertiary amine group) ????3.5
The above results shows that the AB multipolymer of heterocyclic group modification shows better pigment wetting performance, and therefore the reduction with flocculation has improved the dispersion situation.
Under the situation that does not depart from essence of the present invention and protection domain, to those skilled in the art, various modifications, variation, adding or the replacement of present composition component are conspicuous.Illustrative embodiment given herein does not limit the present invention, but limits protection scope of the present invention by claim subsequently.

Claims (16)

1. one kind is suitable for the composition of making pigment dispersing agent, said composition comprises acrylic block copolymer, this multipolymer contains the A segment and relative nonpolar B segment of relative polarity, and wherein the heterocyclic group that comprises of this A segment is selected from: contain at least one monokaryon that is free of attachment to the nitrogen-atoms on the hydrogen atom and/or double-core five and/or six-ring.
2. the composition of claim 1, wherein segmented copolymer prepares by group transfer polymerization (GTP) technology.
3. the composition of claim 1, wherein segmented copolymer is formed by polymeric (methyl) acrylic monomer.
4. the composition of claim 1, wherein segmented copolymer is formed by polymeric methacrylic monomer.
5. the composition of claim 1, the segment that wherein comprises heterocyclic group be by epoxy-functional on the segment and the heterogeneous ring compound prepared in reaction that comprises following functional group, and described functional group is-NH-,-NH 2-,-COOH or-SH.
6. the composition of claim 1, wherein heterocyclic group is connected on the A segment by urea and/or urethane bond.
7. the composition of claim 1, wherein the hydroxyl value of segmented copolymer is 5-120, total number-average molecular weight (Mn) is 1,300-13,000.
8. the composition of claim 1, wherein heterocyclic group is selected from: replace or replace, triazole, pyrimidine, imidazoles, pyridine, morpholine, tetramethyleneimine, piperazine, piperidines, benzoglyoxaline, benzothiazole and triazine.
9. the composition of claim 1, wherein heterocyclic group is an imdazole derivatives.
10. the composition that has the claim 1 of AB configuration, wherein multipolymer only comprises an A segment and B segment that is bonded together.
11. one kind is suitable for the acrylic acid or the like AB block copolymer composition of making pigment dispersing agent, comprises:
Based on the weight of multipolymer, the relative polarity A segment of about 10-30wt%; With
Based on the weight of multipolymer, the nonpolar relatively B segment of about 70-90wt% hydroxyl;
Each segment contains the preferred main chain of mainly being made up of polymeric methacrylic monomeric unit;
The wherein said A segmental methacrylic of 50wt% at least partly contains directly by alkyl chain or is bonded to heterocyclic group on it by urethane and/or urea key indirectly, and described heterocyclic group is selected from and comprises at least one monokaryon that is free of attachment to the nitrogen-atoms on the hydrogen atom and/or double-core five and/or six-ring.
12. the composition of claim 11, wherein heterocyclic group is selected from: do not replace or replace, triazole, pyrimidine, imidazoles, pyridine, morpholine, tetramethyleneimine, piperazine, piperidines, benzoglyoxaline, benzothiazole and triazine.
13. the composition of claim 12, wherein heterocyclic group is an imdazole derivatives.
14. the composition of claim 13, wherein heterocyclic group is glyoxal ethyline or 4-methylimidazole.
15. composition dispersive pigment dispersion in organic solvent that uses claim 1.
16. a coating composition comprises pigment dispersion, membrane-forming agent and the liquid medium of claim 15.
CNB008139415A 1999-10-07 2000-10-04 Acrylic block copolymer pigment dispersants containing beterocyclic groups Expired - Fee Related CN1175007C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/414254 1999-10-07
US09/414,254 US6316564B1 (en) 1999-10-07 1999-10-07 Acrylic block copolymer pigment dispersants containing heterocyclic groups

Publications (2)

Publication Number Publication Date
CN1378564A true CN1378564A (en) 2002-11-06
CN1175007C CN1175007C (en) 2004-11-10

Family

ID=23640630

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB008139415A Expired - Fee Related CN1175007C (en) 1999-10-07 2000-10-04 Acrylic block copolymer pigment dispersants containing beterocyclic groups

Country Status (15)

Country Link
US (1) US6316564B1 (en)
EP (1) EP1228107B1 (en)
JP (1) JP4047583B2 (en)
KR (1) KR100481341B1 (en)
CN (1) CN1175007C (en)
AT (1) ATE299511T1 (en)
AU (1) AU7750600A (en)
BR (1) BR0014723A (en)
CA (1) CA2384775C (en)
DE (1) DE60021278T2 (en)
DK (1) DK1228107T3 (en)
ES (1) ES2244475T3 (en)
MX (1) MXPA02003499A (en)
NZ (1) NZ517591A (en)
WO (1) WO2001025292A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101082684B (en) * 2006-06-02 2011-01-19 富士胶片株式会社 Paint dispersion combination, optical solidification combination, filter produced thereof and producing method
CN1827687B (en) * 2005-03-04 2011-06-08 比克化学股份有限公司 Stabilized unsaturated polyester resin mixtures

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6849679B2 (en) * 2001-05-21 2005-02-01 Ciba Specialty Chemicals Corporation Pigment compositions with modified block copolymer dispersants
KR20050123148A (en) * 2003-04-08 2005-12-29 시바 스페셜티 케미칼스 홀딩 인크. Light stabilising polymer dispersants in pigment dispersions
US7605194B2 (en) * 2003-06-24 2009-10-20 Ppg Industries Ohio, Inc. Aqueous dispersions of polymer-enclosed particles, related coating compositions and coated substrates
US20100184911A1 (en) * 2009-01-22 2010-07-22 Ppg Industries Ohio, Inc. Aqueous dispersions of polymer-enclosed particles, related coating compositions and coated substrates
US7652099B2 (en) * 2005-09-12 2010-01-26 E.I. Du Pont De Nemours And Company Process for producing coating compositions with customizable properties
US8754166B2 (en) * 2005-09-12 2014-06-17 Axalta Coating Systems Ip Co., Llc Coatings system with common activator and common volumetric mix ratio
DE102006021200A1 (en) * 2006-05-06 2007-11-15 Byk-Chemie Gmbh Use of copolymers as adhesion promoters in paints
DE102006062441A1 (en) * 2006-12-27 2008-07-03 Byk-Chemie Gmbh Comb polymer is useful as a wetting agent and dispersant comprises styrene units and derivatized maleic anhydride units with phosphate or quaternary ammonium functions
WO2010036867A1 (en) 2008-09-25 2010-04-01 E. I. Du Pont De Nemours And Company Block copolymer pigment dispersants
US20100081769A1 (en) * 2008-09-26 2010-04-01 E.I.Du Pont De Nemours And Company Process for producing block copolymer pigment dispersants
US20100081752A1 (en) * 2008-09-26 2010-04-01 E. I. Du Pont De Nemours And Company Process for producing block copolymer pigment dispersants
US20100081754A1 (en) * 2008-09-26 2010-04-01 E.I.Du Pont De Nemours And Company Process for producing block copolymer pigment dispersants
US20100081753A1 (en) * 2008-09-26 2010-04-01 E. I. Du Pont De Nemours And Company Process for producing block copolymer pigment dispersants
CN102232090A (en) * 2008-10-03 2011-11-02 凯米利克有限公司 AB diblock copolymers and applications for their use
FR2941704B1 (en) * 2009-01-30 2011-12-23 Arkema France BLOCK COPOLYMERS WITH ASSOCIATIVE GROUPS AND ADHESIVE COMPRISING SAME
US20120029139A1 (en) * 2009-01-30 2012-02-02 Centre National De La Recherche Scientifique (Cnrs Block copolymers having associative groups, and adhesive containing same
JP5552153B2 (en) 2009-03-25 2014-07-16 ビック−ケミー ゲゼルシャフト ミット ベシュレンクテル ハフツング Composition comprising a stable polyol mixture
JP5690355B2 (en) 2009-12-22 2015-03-25 ビック−ケミー ゲゼルシャフト ミット ベシュレンクテル ハフツング Composition comprising a stable polyol mixture
WO2011141745A2 (en) * 2010-05-14 2011-11-17 Fujifilm Imaging Colorants Limited Dispersion, process for preparing a dispersion and ink jet printing ink
MX2012012947A (en) 2010-05-14 2012-12-17 Fujifilm Imaging Colorants Ltd Printing process, polymer and ink.
EP2594613B1 (en) * 2010-07-12 2016-09-21 Hanwha Chemical Corporation Conductive coating composition and method for manufacturing a conductive layer using same
WO2013101856A1 (en) * 2011-12-30 2013-07-04 E. I. Du Pont De Nemours And Company Aqueous pigment dispersions with components to interact with cellulose
ITBO20120066A1 (en) * 2012-02-10 2013-08-11 Consiglio Nazionale Ricerche PROCEDURE FOR THE TREATMENT OF A POLYMER
US20160152859A1 (en) 2013-06-24 2016-06-02 Byk-Chemie, Gmbh Adhesion-strengthening additive and coating composition containing same
EP3029111A4 (en) * 2013-07-31 2017-02-22 Nissan Chemical Industries, Ltd. Carbon material dispersed film formation composition
EP3565865B1 (en) 2017-01-03 2020-10-14 BYK-Chemie GmbH (meth)acrylic copolymers as rheological additives in drilling fluids and drilling fluids comprising such copolymers
KR102090233B1 (en) 2018-11-29 2020-03-17 용인송담대학교 산학협력단 Functional golf inner-wear for improving golf swing trajectory and shot distance

Family Cites Families (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2015132B2 (en) 1970-03-28 1972-10-05 CIRCUIT FOR LINEARIZATION OF A NON-LINEAR CHARACTERISTIC CURVE OF AN ELECTRIC SENSOR
US4032698A (en) 1973-02-02 1977-06-28 E. I. Du Pont De Nemours And Company Polymeric materials with substituted urea end groups
JPS5575414A (en) 1978-11-30 1980-06-06 Nippon Oil & Fats Co Ltd Polymer or copolymer having peroxy bond in molecule
US4508880A (en) 1981-06-30 1985-04-02 E. I. Du Pont De Nemours And Company "Living" polymers and process for their preparation
US4524126A (en) 1981-06-30 1985-06-18 International Business Machines Corporation Adhesion of a photoresist to a substrate
US4417034A (en) 1981-06-30 1983-11-22 E. I. Du Pont De Nemours & Co. Living polymers and process for their preparation
JPS5827716A (en) 1981-08-11 1983-02-18 Asahi Chem Ind Co Ltd Curing agent composition for aqueous dispersion of epoxy resin
US4414372A (en) 1982-06-17 1983-11-08 E. I. Du Pont De Nemours & Co. Process for preparing living polymers
JPS60127325A (en) 1983-12-13 1985-07-08 Sumitomo Chem Co Ltd Manufacture of nylon block copolymer
US4656226A (en) 1985-09-30 1987-04-07 E. I. Du Pont De Nemours And Company Acrylic pigment dispersants made by group transfer polymerization
US4902732A (en) 1985-09-30 1990-02-20 Shin-Etsu Chemical Co., Ltd. Epoxy resin-based curable compositions
US4764632A (en) 1986-01-07 1988-08-16 Cavedon Chemical Company, Inc. Multifunctional amino zirconium aluminum metallo organic complexes useful as adhesion promoter
US4711910A (en) 1986-10-24 1987-12-08 Atlantic Richfield Company Preparation of fire retardant flexible polyester based polyurethane foams having reduced discoloration and scorch
US4755563A (en) 1986-12-29 1988-07-05 E. I. Du Pont De Nemours And Company Block copolymer dispersants containing ionic moieties
US4942213A (en) 1987-12-04 1990-07-17 Byk-Chemie Gmbh Addition compounds useful as dispersing agents and dispersion stabilizers, process for producing them, their use and solids coated therewith
US4812517A (en) 1987-12-28 1989-03-14 E. I. Du Pont De Nemours And Company Dispersants resistant to color change
US4880884A (en) 1988-04-27 1989-11-14 The Dow Chemical Company Poly(aryl ether)-poly(aryl carbonate) block copolymers and their preparation
US5180760A (en) 1988-04-28 1993-01-19 Nippon Oil And Fats Company, Limited Anti-fogging resin film-forming composition
JP2707677B2 (en) 1989-02-02 1998-02-04 日本油脂株式会社 Composition for forming hydrophilic porous film
JP2725342B2 (en) 1989-02-02 1998-03-11 日本油脂株式会社 Coating composition for heat exchanger fin
US5013469A (en) 1989-08-24 1991-05-07 Texaco Inc. VI improver, dispersant, and anti-oxidant additive and lubricating oil composition containing same
CA2033591A1 (en) 1990-01-16 1991-07-17 Casmir S. Ilenda Imidized segmented copolymers
US5085698A (en) 1990-04-11 1992-02-04 E. I. Du Pont De Nemours And Company Aqueous pigmented inks for ink jet printers
RU2050389C1 (en) 1990-06-19 1995-12-20 Научно-производственное акционерное общество "Спектр МС" Method for production of aqueous-dispersion composition for coatings
US5205949A (en) 1991-06-19 1993-04-27 Texaco Inc. Dispersant and VI improver additive and lubrication oil composition containing same
US5205861A (en) 1991-10-09 1993-04-27 E. I. Du Pont De Nemours And Company Aqueous ink jet inks containing alkylene oxide condensates of certain nitrogen heterocyclic compounds as cosolvents
US5298568A (en) 1992-01-31 1994-03-29 Toyo Ink Manufacturing Co., Ltd. Modified olefin resin and resin composition
JPH05230126A (en) 1992-02-25 1993-09-07 Nippon Steel Chem Co Ltd Aromatic hydroxyl group-bearing styrene-based polymer and its production
JPH05271636A (en) 1992-03-30 1993-10-19 Aica Kogyo Co Ltd One-pack epoxy resin adhesive
JPH05295341A (en) 1992-04-16 1993-11-09 Aica Kogyo Co Ltd Expoxy resin adhesive
JPH0693171A (en) 1992-09-09 1994-04-05 Sumitomo Durez Co Ltd Epoxy resin composition of excellent thermal shock resistance
US5648446A (en) 1993-02-24 1997-07-15 Mitsui Toatsu Chemicals, Inc. Diguanamines and preparation process, derivatives and use thereof
US5476544A (en) 1993-02-26 1995-12-19 Toyo Ink Manufacturing Co., Ltd. Water-based pigment dispersion
JPH0711105A (en) 1993-06-22 1995-01-13 Sumitomo Durez Co Ltd Epoxy resin composition with excellent thermal impact property
US5424364A (en) 1994-05-17 1995-06-13 E. I. Du Pont De Nemours & Company Comb pigment dispersants
JPH07331084A (en) 1994-06-02 1995-12-19 Sumitomo Bakelite Co Ltd Thermoplastic elastomer resin composition
TW318861B (en) 1994-08-16 1997-11-01 Mitsui Toatsu Chemicals
JP3175516B2 (en) 1995-01-13 2001-06-11 東洋インキ製造株式会社 Ink jet recording liquid and method for producing the same
DE19505750A1 (en) 1995-02-20 1996-08-22 Basf Ag Agglomerated, finely divided, crosslinked vinylimidazole copolymers, processes for their preparation and their use
JPH0987570A (en) 1995-09-25 1997-03-31 Toyo Ink Mfg Co Ltd Aqueous pigment dispersion
JPH09157394A (en) 1995-12-12 1997-06-17 Honda Motor Co Ltd Aromatic heterocyclic block copolymer, and aromatic heterocyclic block copolymer molding and its production
JPH1017802A (en) 1996-07-08 1998-01-20 Toyo Ink Mfg Co Ltd Ink jet recording fluid and its production
JP2001501653A (en) 1996-09-24 2001-02-06 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ Dispersant viscosity index improver
US5854331A (en) 1997-11-04 1998-12-29 E. I. Du Pont De Nemours And Company Block copolymers of oxazolines and oxazines as pigment dispersants and their use in ink jet inks

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1827687B (en) * 2005-03-04 2011-06-08 比克化学股份有限公司 Stabilized unsaturated polyester resin mixtures
CN101082684B (en) * 2006-06-02 2011-01-19 富士胶片株式会社 Paint dispersion combination, optical solidification combination, filter produced thereof and producing method

Also Published As

Publication number Publication date
KR100481341B1 (en) 2005-04-08
DE60021278D1 (en) 2005-08-18
ES2244475T3 (en) 2005-12-16
ATE299511T1 (en) 2005-07-15
JP4047583B2 (en) 2008-02-13
DE60021278T2 (en) 2006-05-18
EP1228107A1 (en) 2002-08-07
US6316564B1 (en) 2001-11-13
CA2384775C (en) 2010-04-13
DK1228107T3 (en) 2005-09-19
BR0014723A (en) 2002-06-18
NZ517591A (en) 2003-11-28
EP1228107B1 (en) 2005-07-13
CA2384775A1 (en) 2001-04-12
MXPA02003499A (en) 2002-09-02
CN1175007C (en) 2004-11-10
KR20020033841A (en) 2002-05-07
JP2003511490A (en) 2003-03-25
AU7750600A (en) 2001-05-10
WO2001025292A1 (en) 2001-04-12

Similar Documents

Publication Publication Date Title
CN1175007C (en) Acrylic block copolymer pigment dispersants containing beterocyclic groups
AU769161B2 (en) Pigment dispersions containing ABC-block polymer dispersant
CN1117777C (en) Pigment dispensions containing aqueous branched polymer dispensant
KR100453307B1 (en) Dispersions Having Improved Stability
JP3776013B2 (en) Graft copolymer pigment dispersant
CA2104702C (en) Urea-modified copolymer as dispersants for pigments in coating compositions
US6495618B1 (en) Graft copolymer with an amide functional group as a pigment dispersant
JP2002523580A (en) Polymer pigment dispersant having acrylic main chain, polyester side chain, cyclic imide group and quaternary ammonium group
CN1409733A (en) Graft copolymer pigment dispersant
JP2002510353A (en) Pigment dispersion containing hydroxylated AB-block polymer dispersant
US6451950B1 (en) Polymeric pigment dispersants having multiple pigment anchoring groups
US10131750B2 (en) Polymer compositions and use of these polymer compositions as dispersants
US6852803B2 (en) Graft copolymer with a urethane/urea group as a pigment dispersant
US7288589B2 (en) Pigment dispersions for solventborne coatings with improved rheology

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20041110

Termination date: 20141004

EXPY Termination of patent right or utility model